Nonadiabatic Dynamics Simulations for Photoinduced Processes in Molecules and Semiconductors: Methodologies and Applications DOI
Xiang‐Yang Liu, Wenkai Chen, Wei‐Hai Fang

et al.

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(23), P. 8491 - 8522

Published: Nov. 20, 2023

Nonadiabatic dynamics (NAMD) simulations have become powerful tools for elucidating complicated photoinduced processes in various systems from molecules to semiconductor materials. In this review, we present an overview of our recent research on photophysics molecular and periodic materials with the aid ab initio NAMD simulation methods implemented generalized trajectory surface-hopping (GTSH) package. Both theoretical backgrounds applications developed are presented detail. For systems, linear-response time-dependent density functional theory (LR-TDDFT) method is primarily used model electronic structures owing its balanced efficiency accuracy. Moreover, efficient algorithms calculating nonadiabatic coupling terms (NACTs) spin–orbit couplings (SOCs) been coded into package increase efficiency. combination analysis techniques, can explore mechanistic details a range including charge separation energy transfer organic donor–acceptor structures, ultrafast intersystem crossing (ISC) transition metal complexes (TMCs), exciton aggregates. materials, simulating carrier within framework Kohn–Sham (KS-DFT), which SOC effects explicitly accounted using two-component, noncollinear DFT method. Using method, investigated at interface variety van der Waals (vdW) heterojunctions, such as two-dimensional dichalcogenides (TMDs), carbon nanotubes (CNTs), perovskites-related systems. Recently, extended LR-TDDFT-based allowing us study excitonic process. These results demonstrate that exploring photodynamics future studies, be employed elucidate experimental phenomena reveal microscopic well rationally design novel photofunctional desired properties.

Language: Английский

Solution-processed green and blue quantum-dot light-emitting diodes with eliminated charge leakage DOI
Yunzhou Deng, Feng Peng, Yao Lu

et al.

Nature Photonics, Journal Year: 2022, Volume and Issue: 16(7), P. 505 - 511

Published: May 19, 2022

Language: Английский

Citations

324
Efficient energy transport in an organic semiconductor mediated by transient exciton delocalization DOI Creative Commons
Alexander J. Sneyd, Tomoya Fukui, David Paleček

et al.

Science Advances, Journal Year: 2021, Volume and Issue: 7(32)

Published: Aug. 4, 2021

Precisely tuning an organic semiconductor’s crystalline order allows exciton transport to proceed 2-3 orders of magnitude faster.

Language: Английский

Citations

112
Charge Transport in Organic Semiconductors: The Perspective from Nonadiabatic Molecular Dynamics DOI Creative Commons
Samuele Giannini, Jochen Blumberger

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(6), P. 819 - 830

Published: Feb. 23, 2022

ConspectusOrganic semiconductors (OSs) are an exciting class of materials that have enabled disruptive technologies in this century including large-area electronics, flexible displays, and inexpensive solar cells. All these rely on the motion electrical charges within material diffusivity critically determines their performance. In respect, it is remarkable nature charge transport has puzzled community for so many years, even apparently simple systems such as molecular single crystals: some experiments would better fit interpretation terms a localized particle picture, akin to or biological electron transfer, while others agreement with wave-like interpretation, more band metals.Exciting recent progress theory simulation carrier OSs now led unified understanding disparate findings, Account will review one tools developed our laboratory detail: direct propagation by quantum-classical nonadiabatic dynamics. One finds defect-free crystals can either localize molecule substantially delocalize over large number molecules depending relative strength electronic couplings between molecules, reorganization, trapping energy thermal fluctuations site energies, also known electron–phonon couplings.Our simulations predict exhibiting highest measured mobilities date, forms "flickering" polarons, objects delocalized 10–20 average constantly change shape extension under influence disorder. The flickering polarons propagate through OS short (≈10 fs long) bursts wave function lead expansion polaron about twice its size, resulting spatial displacement, diffusion, mobility, conductivity. Arguably best termed "transient delocalization", mechanistic scenario very similar assumed transient localization supports assertions. We applications methodology disordered nanocrystalline samples, which allows us understand defects grain boundaries propagation.Unfortunately, energetically favorable packing structures typical OSs, whether polymeric, places fundamental constraints mobilities/electronic conductivity compared inorganic semiconductors, limits range applications. Account, we design rules could pave way new high-mobility argue 2D covalent organic frameworks most promising candidates satisfy them.We conclude dynamics method powerful approach predicting crystalline materials. close brief outlook extensions exciton transport, dissociation, recombination. This bring step closer birth, survival, annihiliation at interfaces optoelectronic devices.

Language: Английский

Citations

100
Accurate Computation of Nonadiabatic Coupling with Projector Augmented-Wave Pseudopotentials DOI
Weibin Chu, Qijing Zheng, Alexey V. Akimov

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2020, Volume and Issue: 11(23), P. 10073 - 10080

Published: Nov. 12, 2020

Synergy of nonadiabatic molecular dynamics with real-time time-dependent density functional theory has led to significant progress in modeling excited-state nanoscale and condensed matter systems over the past decade. Nonadiabatic coupling (NAC) is central quantity such simulations, its accurate efficient evaluation an enduring challenge Kohn-Sham theory, particularly conjunction planewave basis sets projector augmented-wave (PAW) pseudopotentials because complexity PAW "all-electron" wave function. We report a method for rigorous NAC functions demonstrate approximation that gives comparable accuracy. As validation, we intensely examine matrix elements calculated using both pseudo- all-electron under formalism six representative systems. The approximate obtained pseudowave close exact NAC, largest deviations observed when subshell d-electrons are involved transitions. developed approach provides convenient methodology numerical computation framework.

Language: Английский

Citations

93
CO2 Photoreduction on Metal Oxide Surface Is Driven by Transient Capture of Hot Electrons: Ab Initio Quantum Dynamics Simulation DOI
Weibin Chu, Qijing Zheng, Oleg V. Prezhdo

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(6), P. 3214 - 3221

Published: Jan. 22, 2020

The most critical bottleneck in CO2 photoreduction lies the activation of to form an anion radical, CO2•-, or other intermediates by photoexcited electrons, because has a high-energy lowest unoccupied molecular orbital (LUMO). Taking rutile TiO2(110) as prototypical surface, we use time-dependent ab initio nonadiabatic dynamics simulations reveal that excitation bending and antisymmetric stretching vibrations can sufficiently stabilize LUMO below conduction band minimum, allowing it trap hot electrons get reduced. Such vibrational excitations occur formation transient CO2•- adsorbed oxygen vacancy. for nearly 100 fs dissociate CO within 30-40 after trapping. We propose driven applies reduction photocatalysts be realized different techniques material design.

Language: Английский

Citations

77
Applying Marcus theory to describe the carrier transports in organic semiconductors: Limitations and beyond DOI Open Access
Zhigang Shuai, Weitang Li, Jiajun Ren

et al.

The Journal of Chemical Physics, Journal Year: 2020, Volume and Issue: 153(8)

Published: Aug. 26, 2020

Marcus theory has been successfully applied to molecular design for organic semiconductors with the aid of quantum chemistry calculations parameters: intermolecular electronic coupling V and intramolecular charge reorganization energy λ. The assumption behind this is localized nature state representing carriers, being holes or electrons. As far as quantitative description carrier mobility concerned, direct application semiclassical usually led underestimation experimental data. A number effects going beyond such a will be introduced here, including nuclear effect, dynamic disorder, delocalization effects. recently developed dynamics simulation at time-dependent density matrix renormalization group briefly discussed. latter was shown quickly emerging efficient method complex system.

Language: Английский

Citations

74
Time‐dependent density matrix renormalization group method for quantum dynamics in complex systems DOI
Jiajun Ren, Weitang Li, Tong Jiang

et al.

Wiley Interdisciplinary Reviews Computational Molecular Science, Journal Year: 2022, Volume and Issue: 12(6)

Published: March 21, 2022

Abstract The simulations of spectroscopy and quantum dynamics are vital importance to the understanding electronic processes in complex systems, including radiative/radiationless relaxation relevant for optical emission, charge/energy transfer molecular aggregates related carrier mobility organic materials, as well photovoltaic thermoelectric conversion, light‐harvesting spin transport, so forth. In recent years, time‐dependent density matrix renormalization group (TD‐DMRG) has emerged a general, numerically accurate efficient method high‐dimensional full‐quantum dynamics. This review will cover fundamental algorithms TD‐DMRG modern framework product states (MPS) operators (MPO), basic algebra with respect MPS MPO, novel time evolution schemes propagate MPS, automated MPO construction algorithm encode generic Hamiltonian. Most importantly, proposed can handle mixed state at finite temperature, enabling statistical description aggregates. We demonstrate performance by benchmarking current state‐of‐the‐art methods simulating spin‐boson model Frenkel–Holstein(–Peierls) model. As applications real‐world problems, we present theoretical investigations spectral function rubrene crystal, radiationless decay rate azulene an anharmonic potential energy surface. article is categorized under: Theoretical Physical Chemistry > Statistical Mechanics Reaction Dynamics Kinetics Software Simulation Methods

Language: Английский

Citations

66
A New Frontier in Exciton Transport: Transient Delocalization DOI Creative Commons
Alexander J. Sneyd,

David Beljonne,

Akshay Rao

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2022, Volume and Issue: 13(29), P. 6820 - 6830

Published: July 20, 2022

Efficient exciton transport is crucial to the application of organic semiconductors (OSCs) in light-harvesting devices. While physics highly disordered media well-explored, description structurally and energetically ordered OSCs less established, despite such materials being favorable for In this Perspective we describe highlight recent research pointing toward a efficient mechanism which occurs OSCs, transient delocalization. Here, exciton–phonon couplings play critical role allowing localized states temporarily access higher-energy delocalized whereupon they move large distances. The shows great promise facilitating long-range may allow improved device efficiencies new architectures. However, many fundamental questions on delocalization remain be answered. These suggested next steps are summarized.

Language: Английский

Citations

49
A multi-state mapping approach to surface hopping DOI Creative Commons
Johan E. Runeson, David E. Manolopoulos

The Journal of Chemical Physics, Journal Year: 2023, Volume and Issue: 159(9)

Published: Sept. 7, 2023

We describe a multiple electronic state adaptation of the mapping approach to surface hopping introduced recently by Mannouch and Richardson [J. Chem. Phys. 158, 104111 (2023)]. Our modification treats populations coherences on an equal footing is guaranteed give in any basis that tend correct quantum–classical equilibrium values long-time limit (assuming ergodicity). demonstrate its accuracy comparison with exact benchmark results for three- seven-state models Fenna–Matthews–Olson complex, obtaining are significantly more accurate than those fewest switches at least as good other semiclassical method we aware of. Since these were obtained adapting scheme Richardson, go compare our theirs variety problems two states. find their sometimes accurate, especially Marcus inverted regime. However, situations, accuracies comparable, since can be used states it applied wider electronically nonadiabatic systems.

Language: Английский

Citations

35
Transiently delocalized states enhance hole mobility in organic molecular semiconductors DOI
Samuele Giannini, Lucia Di Virgilio, Marco Bardini

et al.

Nature Materials, Journal Year: 2023, Volume and Issue: 22(11), P. 1361 - 1369

Published: Sept. 14, 2023

Language: Английский

Citations

25